Process for obtaining valuable products from solid carbonachous materials



Dec. 29, 1931. R. T. HASLAM ET AL 1,838,543

PROCESS FOR OBTAINING VALUABLE PRODUCTS FROM SOLID CARBQNACE MATERIALS Filed June 1929 Patented Dec. 29, 1931 UNITED S ATES PATENT OFFICE ROBERT '1. W, 01 WESTI'IELD, NEW .mnsmr, mam-1r L. YOUNG, O! m YORK, N. Y ASSIGNOBS '10 STANDARD-I. G. comm rnocnss 1'03. orummo variants raonuc'rs Immune no! com GAEBOIAOIOUI 'Application'fllcd June 2:, 1m. Serial Io. cram.

Referring to the drawing, reference nu meral 1 denotes a mill of any preferred form adapted to reduce coal or other similar carbonaceous material to a finely divided state and to incorporate the ound coal into a fluid sus nsion in oil which is introduced by line 2. e fluid mass is forcedby pum 3 through line 4 into a hydrogenation 0 am r 5, which is adapted to withstand pressures of to 200 atmospheres or higher when at an elevated temperature of 8 00 to.950 -F.," in the presence of free hydro en; The chamher or drum'may be heated in any preferred manner, such as by means of electric heaters 6 or otherwise,and-the contentsiiskeptm" continual agitation. by means of aistirr ng,

mechanism A gas rich in free'hydrogen the drum byi'pipe 8, and vapor-and gas escape through a vapor line 9 to a-part1alcon-' denser preferably, intheform of a rectifica+ tion tower 10, with cooling coil 11 at the top,

heating coil 12 at the base and bell-cap plate 13, or their equivalent, therebetween. Vapor and gas are conducted to final condenser lei and condensate is separated from gas by; means of a separatordrum 15. The distillate is withdrawn to storage (not shown)-- by line 16 and gas-is removed by line.=.1Z .toa purifier I which my comp-rise any oil'scmbbingii; Purified oil is conducted to a still or other a suitable apparatus for removing the traces of thewlvent. If the solvent used is relasystem or equivalent means ---jfor dissolving the major quantity of hydrocarbonaconstitm ents and hydrogen sulfi'd from thdg'as Puri fie d gas is recompressed by booster 519 and a part is returned by line'20 to drum fi 'after preheating inlcoil 11' and'an exchanger .21

or otherwise.

resh hydrogen-is added by 1111822. p

if joth Condensate from condenser tower 10 is cooled in cooler 23 and discharged into an accumulator 2'; or withdrawn byline 24a tostorage (not shown). ,The accumulator may be held under pressure below drum 5 and'liberated gas is conducted by line 25 to purifier 18, above'described.

While the present process is preferably.

operated onashless or deashed coal or other carbonaceous. material, such materials are not required, and if a material containing mineral matter is used, it is preferred to withdraw a stream of oil from drum 5 by line 26 to eliminate non-carbonaceous ime purities, The withdrawn oil is cooled in exchangers 27 and 21 and gas released from a separation drum 28. Mineral matter is then a separated from the 011 preferably in a continuous or semi continuous manner by a. rc-

tary filter 29 or equivalent centrifugal or set tling means; I The se arated oil may be re turned by line 29at0 rum 5 and may beused {to carr in fresh carbonaceous mattenif dezjsired, utit is preferred to send a. part of the' oil to-accumulator drum 24 by line 29b for further treatment, as will be disclosed.

Oi1' 'i8 -withdrawn from accumulator 24' and forced by pump 30 through a mixer or extractor 31 together with a suitable solvent introduced by means of pump 32 and capable of dissolving I oxygen-containing im urities, particularly. phenolic bodies from t e oil in addition to nitrogenous impurities and other impurities of an asphaltic character. The extracto'rjmayber of any suitable design,

3 making use of the, counter-current princi- =ple'," if desired. Solvent andpurified oil are .separatedin-drum 33and the former is re turned for recirculation by 'line' 34 or discarded or may be treated for the recovery of the extractin apparatus (not shown).

low boiling, a still 35 is preferred, and erwise, then apparatus .will be adapted 'to effect} the separation by means of some other propert of the specific solvent, as will I be understoo Traces of the low boiling solvent are removed by line 36 and separ hydrogenated oil may be used and in "the drawing, vapor and gasare, taken from the drum by vapor pipe 43 to partial condenser 44 and' -final condenser 45. The condensate from condensera is icooled in'cooler -16 and discharged in o -ai'separator drum 47 from which the: .dist'iltate is taken to sto rage (not shown) :by: 'line '48; Lightcondensate from condenser45 is=alsodischarged into a separator 49 from which the oil is taken to separate storag'by; line. 50" and gas from both drums 47 and'49: is conducted by pipe 51 to the purifier l8 for' recirculation. If desired,- the method of recoveryof the oil, shown in Ser. No. 379,914 filed July 22, "1929. by P." L.

Young, may beused. i

In the operation of the present process, coal or other solid carbonaceous material is subjected to the action of hydrogen at a pressure inrconsiderable excess of atmospheric, preferably "froml20' to 200 atmospheres or higher, and .at a temperature from about 600Fi to.about'850 in a primary hydrogenationzone: Under, the influence of such conditions, the solidinaterial is liquefied. Light oil'boiling belowabout400-F. is produce'd'but preferably in relatively small quantities. Middle oil in the form of dist1llate,"is also 'roduced together with heavy liquid'm'aterial from which ash is separated, if ash 'be present in the original solid. The heavy oil maybe recirculated to the primary hydrogenation or=liquefaction zone but it is preferred to pass this oil, either admixed with the middleoil or alone, to an extraction stage in which oxygen-containing impurities,xsuch. as,. for example, phenolic bodies, are removed; Nitrogenous material and asphaltic products may also be extracted. The solvents preferred are low boilingmaterials immiscible with the oil, such as aqueous solutions, caustic; soda, carbonate'or other alkalis, orlalc oho'ls such'as methyl and ethyl or liquid sulfur dioxide, but other solvents suchasglycerine or glycol, preferably with 'water,jor inorganic or organic acids such as acetic ac'id or esters, may be used. I Solvents maybe used successively, if desired, to remove the several impurities above indicated and these extracts may be recovered from the solventsin any. appropriate manner, such as .acidificationofthe alkali ordistillation 0f the solvent.

It is generally advisable to remove traces of the solvents remaining in the oil before the secondary hydrogenation step. This latter step may be carried out in a variety of different ways, either with or without catalytic materials, but their use is of great advantage and they may be suspended in the drum in finely divided form or packed in lump form in the drum. The preferred catalysts are metallic oxides and their mixtures, such as chromium' and molybdenum oxide and oxide of other polyvalent metals. Temperature is generali y from 700 F. to 950 F. and pressure, as before, in considerable excess of atmospheric, preferably from 20 to 200 atmospheres or higher. There is some light oil formation but this is generally and preferably under 15% or 20% or even 5% or 10% of the oil fed when it is desired to make high-grade lubricating oils. remaining 011 is converted, with a small loss in the form of gas, to oil suitable for lubricating purposes and is in every respect equal or superior to the'best grades of petroleum lubricants when reduced to the proper viscosity and flash. It should be noted that operating the secondary hydrogenation process at a relatively higher temperature results in a copious production of low boiling oils which are suitable for motor fuels.

The I This invention is not to be limited by any theory of the mechanism of the process nor by any illustration of the manner in which it is preferably operated but only by the following claims in which it is desired to claim all novelty inherent in the invention.

' We claim:

1. An improved process for obtaining valuable products from solid carbonaceous materials, comprising liquefying such solid material under the influence of hydrogen at a pressure in considerable excess of atmospheric pressure and at an elevated temperature, contacting a part of the liquefied product with a solvent capable of removing a substantial portion of the oxygen-containing impurities, subsequently subjecting the purified oily product to hydrogenation treatment and recovering a fraction suitable for lubricating purposes there from.

2. An improved process for producing valuable heavy oil from coal, comprising subjecting finely divided coal to treatment with a gas rich in free hydrogen under pressure in considerable excess of atmospheric pressure at an elevated temperature, withdrawing a heavy oily material, removing inor anic material therefrom, washing the oil w1th a substantially immiscible solvent capable of removing oxygencontainin impurities therefrom, subjecting the oil su stantially free of oxygen-containing impurities to a second treatment with a gas rich in free hydrogen at pressure in considerable excess of atmospheric and at an elevated temperature and perature.

recovering an oil suitable for lubricating purposes therefrom.

3. Process according to claim 2 in which the first hydrogenation treatment is in the absence of a catalyst and the second hydrogenation treatment is in the presence of a suitable catalyst.

4. Process according to claim 2 in which pressure during the hydrogenation steps is in excess of about 20 atmospheres, temperature in the first of such steps is from about 600 to 850 F. and temperature in the second of such steps is from about 700 F. to about 950 F.

5. Process according to claim 2 in which traces of the solvent are removed from the oil prior to the second hydrogenation step.

6. An improved process for obtainingincreased yields of valuable lubricants. from coal and other solid carbonaceous materials,

comprising the ste s of liquefying the solid material by the actlon of hydrogen at a pressure above about 20 atmospheres and at a temperature between about 600 and 850 F. interadjusted with pressure whereby phenolic bodies are unreduced, removing such phenolic impurities from the liquefied product and subjecting the purified oil to a second stage of hydrogenation whereby the oil is further refined for lubricating purposes.

7. Process according to claim 6 in which the first hydrogenation step is carried out without the aid of catalysts and the second hydrogenation step is accomplished under the influence of a suitable catalyst immune to sulfur poisoning.

8. Process according to claim 6 in which a pressure of about 200 atmospheres is employed in the liquefaction stage and temperature is adjusted to a point where liquefaction is rapid, but below the phenol reducing tem- ROBERT T. HASLAM. PHILIP L. YOUNG. 

